EP0650967B1 - Procédé de préparation d'alkylaluminoxanes sur support inerte - Google Patents
Procédé de préparation d'alkylaluminoxanes sur support inerte Download PDFInfo
- Publication number
- EP0650967B1 EP0650967B1 EP94113747A EP94113747A EP0650967B1 EP 0650967 B1 EP0650967 B1 EP 0650967B1 EP 94113747 A EP94113747 A EP 94113747A EP 94113747 A EP94113747 A EP 94113747A EP 0650967 B1 EP0650967 B1 EP 0650967B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkylaluminoxanes
- process according
- water
- aluminum
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000012876 carrier material Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- -1 cyclopentadienedienyl Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000006653 Ziegler-Natta catalysis Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
- C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/246—Stationary reactors without moving elements inside provoking a loop type movement of the reactants internally, i.e. the mixture circulating inside the vessel such that the upward stream is separated physically from the downward stream(s)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Definitions
- Alkylaluminoxanes especially methylaluminoxane, win increasingly important as an essential component of a new generation of catalyst systems for manufacturing of polyolefins ("Single Site Catalysts").
- These new ones Catalysts consist essentially, as already made of classic Ziegler-Natta catalysis known from a transition metal compound as a catalyst and the beginning mentioned alkylaluminoxane as an organoaluminum cocatalyst component.
- a transition metal compound preferably cyclopentadienedienyl, indenyl or fluorenyl derivatives Group IVa of the Periodic Table of the Elements.
- alkylaluminoxane required in relation to the transition metal component
- alkylaluminoxane to inert support materials, preferably SiO 2 (JCW Chien, D. He, J. Polym. Science Part A, Polym. Chem ., Vol. 29, 1603-1607 (1991).
- Such supported materials also have the advantage of being easy to separate in condensed phase polymerizations (production of high-purity polymers) or of being usable as free-flowing powders in modern gas-phase processes, the grain morphology of the polymer
- fixed alkylaluminoxanes as dry powders are physically more stable than solutions with a comparable Al content, especially for methylaluminoxane, which, as already mentioned, tends to gel in a toluene solution after a certain storage time .
- EP 0 369 675 (Exxon Chemical) describes a process in which the immobilization of alkylaluminoxanes by reacting an approximately 10% solution of trialkylaluminum in heptane with hydrated silica (8.7 wt .-% H 2 O) is reached.
- Immobilization is described in EP 0 442 725 (Mitsui Petrochemical) by reacting a toluene / water emulsion with an approx. 7% solution of trialkylaluminum in toluene in Presence of silica at temperatures from -50 ° C to +80 ° C causes.
- the object of the present invention was therefore to achieve this To overcome disadvantages of the prior art and one To provide methods by means of which alkylaluminoxanes in high yield and homogeneity in a reproducible way can be fixed on inert carrier materials, wherein the degrees of loading can be varied within wide limits, the grain morphology of the carrier is retained and the products are ultimately available as free-flowing powders.
- the invention relates to a method for producing of alkylaluminoxanes immobilized on inert carrier materials, which is characterized in that to Solutions of alkyl aluminum compounds in hydrocarbons water is dosed in a static mixer and the resulting in the form of dispersions, that is, lyophilic dispersions in the sol state, (cf. Römpp Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, New York 1990, p. 2299 ff) on inert Carrier materials are fixed.
- Another object of the invention are on carrier materials fixed aluminoxanes, prepared according to the invention Method.
- the dispersions used according to the invention can be produced by conventional hydrolysis processes of alkyl aluminum compounds in hydrocarbons as solvents.
- the molar ratio of water to alkyl aluminum compounds is in the range from 0.8: 1 to 1.3: 1, preferably 0.9: 1 to 1.2: 1.
- a method of production is preferred at which water to a solution of trialkyl aluminum in an aliphatic, cycloaliphatic or preferably aromatic hydrocarbon through a mixing nozzle into a static mixer, preferably one Beam loop reactor (SSR), is dosed (European patent application No. 93118245.5).
- SSR Beam loop reactor
- In the method according to the invention is in a volume flow ratio from 1: 2,000 to 1: 40,000, preferably 5000 - 20000, water into the jet loop reactor via the mixing nozzle dosed.
- the jet loop reactor ensures because of the high circulation flow for a good and extremely fast mixing of the solution containing aluminum alkyl with water. Due to the high primary dispersion can be a locally too high concentration of water can be avoided, which otherwise lead to loss of yield due to the formation of aluminum hydroxide on the one hand and an undesirably high proportion of unconverted Aluminum trialkyl on the other hand, leads.
- the average degree of oligomerization n which is expressed in the average molecular weight of the reaction product, can be influenced in a targeted manner by suitable metering of the reactants and control of the reaction parameters.
- the molar ratio of H 2 O / aluminum trialkyl, in particular also in the case of trimethyl aluminum (TMA), can be set to the desired value. This is of particular importance since the activity of aluminoxanes as cocatalyst in olefin polymerization apparently depends on the degree of oligomerization of the aluminoxane used (Lit.:.W. Kaminsky, Nachr. Chem. Tech. Lab. 29, 373-7 (1981); W. Kaminsky et al., Makromol. Chem., Macromol. Symp. 3, 377-87 (1986)).
- Trialkylaluminum compounds are preferred according to the invention with short-chain alkyl radicals, especially methyl radicals.
- the carrier materials which can be used according to the invention are the porous oxides of one or more of the elements of groups II, III or IV of the periodic table, such as ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, preferably Al 2 O 3 and MgO and in particular SiO 2 , used.
- These carrier materials can have grain sizes in the range from 1 to 300 ⁇ m, preferably 10 to 200 ⁇ m; Surfaces of 10-1000 m 2 / g, in particular 100-500 m 2 / g; N 2 pore volumes of 0.5-3 cm 3 , preferably 1-2 cm 3 .
- the water content of the carrier materials should be ⁇ 5% by weight, preferably ⁇ 3% by weight and in particular ⁇ 1% by weight. in the If necessary, the commercially available carrier materials therefore before use at temperatures of 150 - 1000 ° C, preferably 200 - 500 ° C, 2 - 20 hours, if necessary at reduced pressure, dried.
- the application and fixation of the aluminoxanes to the carrier materials takes place according to known methods either by continuous or portionwise addition of the carrier material to the submitted dispersions under simultaneous homogenization of the mixture, or by Synthesis of the dispersions directly in the presence of the carrier. These mixtures then become the solvent, if appropriate under reduced pressure.
- the original grain morphology of the carrier material is not changed by this procedure.
- the ratio of carrier to aluminoxane is relative within further limits can be varied, according to the invention it is so chosen that on the resulting free-flowing powder from carrier material and aluminoxane 5-40% by weight, preferably 10 - 25 wt .-% aluminum, in the form of aluminoxanes are available (see examples).
- the method according to the invention enables production of supported aluminoxanes with almost quantitative yields of immobilized aluminum, based on the used Trialkylaluminium compounds without technically complex Procedural steps. Due to specifically adjustable Show parameters and reproducible process conditions these supported with the inventive method Alkylaluminoxanes, especially methylaluminoxane, high activities as cocatalysts and are therefore excellently suited for the further production of Catalyst systems for olefin polymerization.
- a dispersion made with the jet loop reactor from 2.92 kg trimethylaluminum (TMA) (aluminum content: 36.8%), 0.58 kg water and 21.5 kg toluene (ratio H 2 O / TMA 0.8) was in a 40 1 steel reactor with 2.0 kg of silica support material (surface (N 2 -BET): 316 m 2 / g; N 2 pore volume: 1.55 ml / g; particle size distribution: 20 - 80 ⁇ m; residual water content: 2 , 6%) stirred and concentrated to dryness under vacuum at room temperature.
- TMA trimethylaluminum
- ratio H 2 O / TMA 0.8
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Claims (8)
- Procédé pour la fabrication d'alkylaluminoxanes immobilisés sur des matériaux de support inertes, caractérisé en ce que l'on ajoute de l'eau de manière dosée à des solutions de composés alkylaluminium dans des hydrocarbures, et en ce que les alkylaluminoxanes résultants, présents sous forme de dispersions, sont fixés sur des matériaux de support inertes.
- Procédé selon la revendication 1, caractérisé en ce que l'on utilise des dispersions de méthylaluminoxanes dans des hydrocarbures aromatiques.
- Procédé selon les revendications 1 et 2, caractérisé en ce que l'eau et les composés alkylaluminium sont mis en oeuvre dans des rapports molaires de 0,8 - 1,3, de préférence de 0,9 - 1,2.
- Procédé selon la revendication 1, caractérisé en ce que l'on utilise comme matériau de support du SiO2 d'une teneur en eau < 5, de préférence < 3% en poids.
- Procédé selon les revendications 1 à 4, caractérisé en ce que 5 - 40, de préférence 10 - 25% en poids d'aluminium est fixé sur le matériau de support sous la forme d'aluminoxanes.
- Procédé selon les revendications 1 à 5, caractérisé en ce que le matériau de support est ajouté de manière dosée à la dispersion.
- Procédé selon les revendications 1 à 5, caractérisé en ce que le matériau de support est déjà présent dans le mélange pendant la préparation de la dispersion.
- Cocatalyseur, consistant en alkylaluminoxanes immobilisés sur des matériaux de support inertes, fabriqué selon l'un quelconque des procédés conformément aux revendications 1 à 7.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4336659A DE4336659A1 (de) | 1993-10-27 | 1993-10-27 | Verfahren zur Herstellung von Alkylaluminoxanen auf inerten Trägermaterialien |
DE4336659 | 1993-10-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0650967A1 EP0650967A1 (fr) | 1995-05-03 |
EP0650967B1 true EP0650967B1 (fr) | 1998-11-18 |
Family
ID=6501148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94113747A Expired - Lifetime EP0650967B1 (fr) | 1993-10-27 | 1994-09-02 | Procédé de préparation d'alkylaluminoxanes sur support inerte |
Country Status (7)
Country | Link |
---|---|
US (1) | US5446001A (fr) |
EP (1) | EP0650967B1 (fr) |
JP (1) | JPH07188253A (fr) |
CA (1) | CA2127671C (fr) |
DE (2) | DE4336659A1 (fr) |
FI (1) | FI115398B (fr) |
NO (1) | NO304692B1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6781007B2 (en) | 2001-12-11 | 2004-08-24 | Crompton Gmbh | Process for preparing partial hydrolysates of organometallic compounds or transition metal catalysts immobilized on inert support materials |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW454020B (en) * | 1994-08-09 | 2001-09-11 | Mitsui Chemicals Inc | Olefin polymerization catalyst |
MX9703592A (es) * | 1994-11-17 | 1997-08-30 | Dow Chemical Co | Componente de catalizador soportado, catalizador soportado, su preparacion y proceso de polimerizacion por adicion. |
US6043180A (en) * | 1994-11-17 | 2000-03-28 | The Dow Chemical Company | Supported catalyst component, supported catalyst, their preparation, and addition polymerization process |
US7153909B2 (en) * | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
CA2163681C (fr) * | 1995-11-24 | 2007-02-13 | Daryll G. Harrison | Catalyseur a base de monocyclopentadienylzirconium |
EP0796859B1 (fr) * | 1996-03-19 | 2002-07-31 | Crompton GmbH | Formulations homogènes et stables de composés organométalliques sensibles à l'oxydation dans des paraffines et procédé de leur préparation |
US5990035A (en) * | 1997-10-21 | 1999-11-23 | Koeppl; Alexander | Polymerization catalyst systems, their preparation, and use |
US7220804B1 (en) | 2000-10-13 | 2007-05-22 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
DE10348624A1 (de) * | 2003-10-15 | 2005-05-25 | Basell Polyolefine Gmbh | Geträgerte Metallalkylverbindung und Verfahren zu deren Herstellung |
EP1805226A1 (fr) | 2004-10-29 | 2007-07-11 | Exxonmobil Chemical Patents Inc. | Compose catalytique contenant un ligand tridente divalent |
WO2010144130A1 (fr) * | 2009-06-11 | 2010-12-16 | W.R. Grace & Co. -Conn. | Procédé de fabrication d'un aluminoxane et catalyseurs comprenant l'aluminoxane ainsi préparé |
WO2011078923A1 (fr) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Procédés pour produire des systèmes de catalyseur |
JP2013166876A (ja) * | 2012-02-16 | 2013-08-29 | Mitsui Chemicals Inc | オレフィン重合用触媒、シート状オレフィン系重合体およびその製造方法、ならびに該シート状オレフィン系重合体を含んでなる成形体 |
US9650453B2 (en) * | 2012-12-28 | 2017-05-16 | Univation Technologies, Llc | Methods of integrating aluminoxane production into catalyst production |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0578838A1 (fr) * | 1992-04-29 | 1994-01-19 | Hoechst Aktiengesellschaft | Catalysateur de polymérisation d'oléfines, procédé pour sa préparation et son utilisation |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4426317A (en) * | 1982-11-24 | 1984-01-17 | Cities Service Company | Process for making olefin polymerization catalyst |
US4730072A (en) * | 1986-08-15 | 1988-03-08 | Shell Oil Company | Process for preparing aluminoxanes |
DE3789666T2 (de) * | 1986-12-30 | 1994-08-04 | Mitsui Petrochemical Ind | Fester katalysator für die olefinpolymerisation und verfahren zu dessen herstellung. |
JPH0742301B2 (ja) * | 1987-02-14 | 1995-05-10 | 三井石油化学工業株式会社 | 微粒子状アルミノオキサン、その製法およびその用途 |
JP2538588B2 (ja) * | 1987-04-03 | 1996-09-25 | 三井石油化学工業株式会社 | オレフイン重合用固体触媒の製法 |
US5026797A (en) * | 1987-10-22 | 1991-06-25 | Mitsubishi Petrochemical Co., Ltd. | Process for producing ethylene copolymers |
EP0315234A1 (fr) * | 1987-10-26 | 1989-05-10 | Texas Alkyls, Inc. | Procédé de préparation d'aluminoxanes |
US4772736A (en) * | 1987-11-23 | 1988-09-20 | Union Carbide Corporation | Process for the preparation of aluminoxanes |
US4937217A (en) * | 1987-12-17 | 1990-06-26 | Exxon Chemical Patents Inc. | Method for utilizing triethylaluminum to prepare an alumoxane support for an active metallocene catalyst |
US4904631A (en) * | 1988-11-08 | 1990-02-27 | Exxon Chemical Patents, Inc. | Supported vanadium catalyst for polymerization of olefins and a process of preparing and using the same |
US4908463A (en) * | 1988-12-05 | 1990-03-13 | Ethyl Corporation | Aluminoxane process |
JP2826362B2 (ja) * | 1990-02-13 | 1998-11-18 | 三井化学株式会社 | オレフィン重合用固体触媒の製造方法、オレフィン重合用固体触媒およびオレフィンの重合方法 |
US5308816A (en) * | 1991-05-31 | 1994-05-03 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization solid catalyst, olefin polymerization catalyst and olefin polymerization |
KR950014847B1 (ko) * | 1992-01-23 | 1995-12-16 | 미쓰이세끼유 가가꾸고오교오 가부시끼가이샤 | 에틸렌계 공중합체의 제조방법 |
EP0567952B1 (fr) * | 1992-04-29 | 1997-12-03 | Hoechst Aktiengesellschaft | Catalyseur de polymérisation d'olefins, procédé pour sa préparation et son utilisation |
-
1993
- 1993-10-27 DE DE4336659A patent/DE4336659A1/de not_active Withdrawn
-
1994
- 1994-03-16 US US08/213,946 patent/US5446001A/en not_active Expired - Fee Related
- 1994-07-08 CA CA002127671A patent/CA2127671C/fr not_active Expired - Fee Related
- 1994-09-02 EP EP94113747A patent/EP0650967B1/fr not_active Expired - Lifetime
- 1994-09-02 DE DE59407302T patent/DE59407302D1/de not_active Expired - Fee Related
- 1994-10-25 JP JP6260617A patent/JPH07188253A/ja active Pending
- 1994-10-25 NO NO944011A patent/NO304692B1/no unknown
- 1994-10-26 FI FI945043A patent/FI115398B/fi not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0578838A1 (fr) * | 1992-04-29 | 1994-01-19 | Hoechst Aktiengesellschaft | Catalysateur de polymérisation d'oléfines, procédé pour sa préparation et son utilisation |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6781007B2 (en) | 2001-12-11 | 2004-08-24 | Crompton Gmbh | Process for preparing partial hydrolysates of organometallic compounds or transition metal catalysts immobilized on inert support materials |
Also Published As
Publication number | Publication date |
---|---|
FI945043A0 (fi) | 1994-10-26 |
EP0650967A1 (fr) | 1995-05-03 |
CA2127671C (fr) | 1999-03-16 |
NO944054D0 (no) | 1994-10-25 |
FI945043A (fi) | 1995-04-28 |
US5446001A (en) | 1995-08-29 |
CA2127671A1 (fr) | 1995-04-28 |
DE4336659A1 (de) | 1995-05-04 |
JPH07188253A (ja) | 1995-07-25 |
NO944054L (no) | 1995-04-28 |
NO304692B1 (no) | 1999-02-01 |
FI115398B (fi) | 2005-04-29 |
DE59407302D1 (de) | 1998-12-24 |
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